Electrolyzing brines



Feb. 17,1942; G. w. HEISE ET 2,273,797

ELECTROLYZING BRINES Original Filed Dec. 31, 1936 FIG.I

INVENTORS GEORGE W HE ISE ERWIN AJSCHUMACHER BY M ATTORNEY Patented Feb. 17, 194;

UNITED STATES PATENT OFFICE ELECTROLYZ ING BRINES I George Heise, Rocky River, and Erwin A.

Schumacher, Lakewood, Ohio, assignors to National Carbon Company, Inc., a corporation of New York Original application December 31, 1936, Serial No.

118,472. Divided and this application December 17, 1938, Serial No. 246,279

The invention relates to electrolytic processes wherein an impressed electric current is passed through a cell having electrodes immersed in an aqueous electrolyte. This application is a division of our application Serial No. 118,472, filed Decemben3l, 1936;

In its broad aspect, the invention comprises -the use of porous electrodes to achieve one or more of the following objects: 1

\ (a) To decrease the voltage drop through, and y the power consumption of, the cell;

(b) To provide for the introduction of one or more chemical reactants into the cell;

(c) To provide a situs for desired chemical reactions;

(d) To provide for the removal of one or more products from the cell, in some instances in relaof a porous or foraminous bodyof conductive.

material, preferably carbon, the dimensions of the pores and inner passages being extremely minute. as further described below.

We are aware that it has been heretofore proposed to use carbon electrodes possessing some permeability to fluids, in various electrolytic processes in an attempt to achieve one or more of the above objects; but none of these proposals has been capable of satisfactory practical application. We have found thatmany of the dimculties experienced by prior workers may be overcome by the use of an improved electrode material. Specifically, we have found that the electrode material should have a porosity above 35% (preferably between 40% and 70%), calcu-' lated as follows: porosity=100 (real density-apparent density) +real density. Further,

the electrode material should have an air permeability above 15, and preferably above 30. Whenever used herein and in the appended claim, the

' term air permeability means the number of 1 Claim. ((1204-98) I permeability of ordinary electrode carbons (types 1, 2, and 3) and of-the special electrode carbons included in this invention (types 4, 5, 6, and 7).

Air perme- '1ype Porosity abmty Per cent We have also found that the pores of the electrode material should be relatively minute and uniformly distributed, and not large, scattered voids and fissures. Material having the latter kind of pores might be described as "leaky rather than porous. The relative uniformity of distribution of the pores in the two kinds of materials may be distinguished by a simple test: if air is forced through a thin block of the material under water, at about the minimum air pressure required to obtain bubbles in the water,

the porous material gives forth a cloud of small bubbles over its entire surface, while the leaky material gives a number of separate 5 streams of bubbles issuing from the larger fissures and voids.

Another test for uniformity of porosity of these materials comprises determining the flow of a viscous liquid, such as a concentrated aqueous solution of cane sugar, under a moderate pressure, for instance a head of about six inches, through a thin (e. g. one-eighth inch) section of the material. Any relatively large fissures permit flow of the solution and are thereby made evident.

Porous electrode material within this invention may be made from comminuted solid carbonaceous material (i'di' example, coke, graphite, or charcoal) and a porous carbonaceous binder (for instance, baked tar or pitch). Suitable methods for making such electrode material are described in U. S. Patent 1,988,478, issued on January 22, 1935, to B. E. Broadwell and L. C.

Werking.

In some processes the kind of solid carbon chosen for the electrode material will make little or no diiference; in other processes it will be desirable or necessary to take advantage of the fact that graphite has a higher oxygen overvoltage than coke, and that coke has a higher oxygen overvoltage than charcoal. Otherwise stated, in a given instance either a high or a low overvoltage may be influential, and the overvoltage characteristics may be accordingly controlled by a proper choice of electrode material.

The practical application of the above-described new electrode material to electrolytic processes, according to this invention. will be described in connection with the attached drawing, in which.

Fig. 1 represents diagrammatically in vertical cross-section an electrolytic cell container i containing an electrolyte II in whichare immersed a porous electrode l2 and a nonporous electrode l3, and

Fig. 2 represents diagrammatically in vertical cross-section an electrolytic cell similar to that shown in Fig. 1 except that it contains two porous electrodes i2 and 22.

The device illustrated inFigure 1 may be used I in cases where it is desired to introduce one or more reactants into the cell, or to remove one' or more reaction products from the cell, through only one electrode.

Examples of processes in which a reactant may advantageously be introduced into the cell through a single electrode i2 involve the electrowinning of copper and zinc with the assistance of sulfur dioxide acting as an anodic depolarizer and leach-liquor regenerator.

Oxydic copper ores (or dead roasted sulfide ores of copper) may be leached with a dilute solution of sulfuric acid, yielding an acid solution containing dissolved copper sulfate. The resulting solution may be electrolyzed to yield copper at the cathode and sulfuric acid at'the anode, the voltage required for electrolysis being usually between 2.1 and 2.3 volts, depending upon the anode material. It has been proposed to reduce the required voltage by introducing an anodic depolarizer, such as sulfur dioxide; but no entirely successful means for doing this has been provided. According to the present invention, depolarization may be accomplished by introducing gaseous sulfur dioxide into the cell through a porous anode l2, as shown in Figure 1. The rate of addition of sulfur dioxide is preferably so adjusted that little or no unoxidized gas remains in the electrolyte within the cell. Experiments have shown that, when the porous carbon electrode described above is used, a cell operating voltage of approximately 0.6 to 1 volt may be attained. It is necessary, of course, to prevent flooding of the electrode well II with electrolyte in this instance, and this may conveniently be accomplished by waterproofing the inner surface of the well l'l, using the waterproofing treatment described, for example, in our Patent 2,017,280. Under some circumstances it will be desirable to use waterproofing solutions which are considerably more concentrated than those mentioned as specific examples in this patent.

In the electrolytic process described above, the copper-containing liquor ll may be introduced into the cell Ill through a conduit H'; the gaseous sulfur dioxide may be introduced through a conduit l6 and the porous anode l2, preferably provided with an inner well I1; the copper is deposited at the cathode l3'; and regenerated leach liquor (exhausted electrolyte) may be removed from the cell through a conduit l5.

1 Another method of introducing the sulfur dioxide into the anolyte, and this latter method enjoys several advantages over the one just described, including the advantage that the anode is not waterproofed, comprises dissolving the sulfur dioxide in a portion, or all, of the fresh,

copper-containing electrolyte, introducing theresulting solution into the cell I0 through the conduit I4, and removing the exhausted electrolyte through the anode l2 and conduit l6. Experiment has shown that this method results in a relatively low cell voltage drop of about 0.6 to 0.9 volt if a porous carbon anode is used; but has the disadvantage of permitting sulfur dioxide to escape from the surface of the electrolyte Ii into the atmosphere, thereby producing unhealthy and obnoxious working conditions in the cell room.

A third method, which we prefer over those described above, comprises dissolving sulfur dioxide in a portion, or all, of the fresh, coppercontaining electrolyte; introducing the resulting solution into the cell I!) through the conduit 16 and the porous anode l2; depositing the copper at the solid cathode l3; and removing the exhausted electrolyte through a conduit l5 or I 4. Experiment has demonstrated that free sulfur dioxide may readily be prevented from reaching the surface of the electrolyte H within the cell, and that a cell voltage drop of only about 0.6 to 0.9 volt may be attained, if a porous carbon anode is used.

Basic and oxydic ores of zinc, such as smithsonite, zincite and calamine, or dead roasted sulfides, may be leached with a dilute sulfuric acid solution to yield an acid solution containing dissolved zinc sulfate, and this liquor may be electrolyzed to yield zinc metal, in a manner analogous to the treatment of oxydic copper ores. The voltage drop through the cell is usually about 3.3 to 3.7 volts. By the use of a porous carbon anode, and the introduction of sulfur dioxide in the first and third ways described above in connection with copper electrolysis, the voltage drop through the cell may be lowered to about 2 to 3 volts, as we have determined by experimentation.

Various attempts have been made in the past to recover copper from reduced ores by leaching with cupric chloride and subsequently electrolyzing the leach liquor. In the so-called Hoepfner process, ore leaching proceeds as follows:

CuzS+2CuClz=4CuCl+S Deposition of the copper from a cuprous salt requires one-half the energy required to deposit it from a cupric salt. Moreover, the cuprous chloride acts as an anodic depolarizer, thereby reducing the required cell voltage. However, heretofore, difliculties with diaphragms and low current efilciencies liave hindered the commercial development of the process.

We have discovered by experiment that the porous carbon electrode of this invention may be utilized to overcome the above-described difllculties. Referring to Figure 1, the copper-rich leach liquor l I, containing cuprous chloride and sodium chloride, may be introduced into a cell ill-through a conduit I4; copper may be deposited at a solid cathode l3; and anolyte containing the cupric chloride formed during the depolarization carbon anode l2 and a suitable conduit IS. A voltage drop through the cell as low as 0.6 volt, and a current efficiency better than 90%, may be obtained.

The invention is not limited to processes involving only inorganic reactants. For instance, if the electrolyte ll contains a halide,

such as potassium bromide, and if an unsaturated aliphatic hydrocarbon, ethylene for instance, is passed into the cell i through a porous carbon anode l2, aliphatic halides and halohydrins may be formed: ethylene dibromide and bromhydrin in the examplecited.

The specific examples described above illustrate typical processes wherein we employ a porous anode and a solidcathode. It will frequently be desired, of course, to use a solid anode and a porous cathode. For instance, the latter arrangement may be used to advantage in the cathodic reduction of nitrobenzene to p-amino-v with a well 23 and a conduit 2|. The overall reaction may be represented as:

The use of two porous electrodes not only eliminates the need for diaphragms, but also provides a continuous process. A further advantage is that the ferricyanide is obtained in a concentration greater than that of the ferrocyanide. We

have found by experiment that an anodic oxidation emciency of 80% or better is obtainable- A further example is provided in the process wherein sulfur dioxide is passed through a porous anode into an electrolyte and chlorine is passed through a porous cathode into the electrolyte. Sulfuric acid is formed at the anode, and hydrochloric acid at the-cathode. This process may be operated to deliver power, and when current phenol. In such a process, a cell Ill may be used which includes a solid anode l3- and a porous carbon cathode l2, which are immersed in a suitable electrolyte II, 'for instance a normal solution of sulfuric acid. Nitrobenzene may be introduced into the cell through the cathode I2. I

At the cathode, the nitrobenzene is reduced cathodically to p-aminophenol which rises to the top of the electrolyte where it may be collected and removed. 3

Another process employing a porous cathode comprises electrolyzing sodium chloride brine in a cell l0 and passing nitric acid into the cell through a porous carbon cathode l2. Nitric acid depolarizes the cathode to form nitric oxide, and

' the cell reactions may be written:

. carbon cathode, as illustrated in Figure 2. -For instance, a sodium sulfate solution may be electrolyzed to produce sulfuric acid at the anode and sodium hydroxide at the cathode, according The sodium sulfate solution may be placed in a cell HI through a suitable conduit l4; anolyte containing the sulfuric acid may be withdrawn through a porous carbon anode 22 and a conduit 2|; and catholyte containing the caustic soda may be withdrawn through a porous carbon cathode l2; thereby eliminating the two diaphragms from an extemal source is introduced 'the rate of. output of products is increased.

Other embodiments of the invention are contemplated by us. For instance, polarization "at either or both of the electrodes, which increases the resistance and opposes the flow of electric current, may be diminished by passing a fluid, which may be either a liquid or a gas, through the porous electrode into the cell or by withdrawing electrolyte from the cell through the porous electrodes, thereby mechanically decreasing the said concentration of material next to the electrode.

In certain processes, for instance in the electrolysis of sodium chloride brine to produce chlobe withdrawn through a porous carbon anode l2 provided with a well l1 and a conduit l8; and catholyte containing potassium hydroxide and unoxidized ferrocyanide may be withdrawn rine at the anode, it'is desired to maintain a maximum concentration of fresh electrolyte in the anolyte. ,By passing brine through a porous anode l2 (Figure 1) into a cell Ill containing the electrolyte II and a cathode l3, the anolyte is continually fed with fresh brine, thereby minimizing the formation. of oxygen or oxygenated chlorine products andthereby also minimizin the rate and severity of the attack on the anode ,material. Furthermore, if air or oxygen is blown through the porous carbon cathode intothe cell,

depolarization of the cathode will reduce the power consumption of the cell; alternatively, catholyte containing the caustic soda may be withdrawn through a porous cathode, thereby eliminating the necessity for the customary diaphragm.

It will be observed that in a number of the processes given as examples herein the attack and disintegration of electrode material by the electrolyte, or products or by-products of electrolysis, is prevented or hindered either by rapid removal of-the corrosive material from contact with the porous electrode, or by preventing the formation of such materials by a depolarization reaction, or by making the depolarizing substance act as the electrochemically active electrode. Therefore, it has been found that the porous carbon electrodes are characterized by a long service life, even in many processes wherein carbon and graphite electrodes have notbeen used successfully heretofore.

It will also be observed that, whenever a material is introduced into the cell through a porous electrode, the electrode serves as an emcient distributor of such material. An eii'ect of the extended nature and chemical composition of the surface 'of these porous carbon electrodes which is often'observed is to promote certain reactions, and one beneficial practical result is an increased efliciency of depolarization. Thus, in

a given instance the porous carbon electrodevention is not limited to that or any other spe-- cific shape. For instance, under some circumstances it may be desired to providenon-porous portions in the electrode, or to adopt a special shape, in order to regulate the distribution of fluid flowing throughthe electrode, or for another reason. It may ,also be advantageous to place a porous electrode orelectrodes, not provided with a central well H or 23,v at the end or ends of the cell container It in such a manner that a space is left between the electrode and the container, which space may be used to serve the functions of the central well I! or 23 described herein.

We claim:

Process for electrolyzing brine which comprises passing the brine through a porous anode into an electrolytic cell containing said anode and a 5 porous cathode and means for withdrawing catholyte through the cathode, said porous anode and porous cathode having an effective surface area in contact with the electrolyte many times greater than their superficial areas, having only mi- 1 nute pores distributed uniformly throughout, and

consisting essentially of carbon; and passing an electric current through the anode, cathode, and brine, whereby caustic alkali is formed at the cathode; and withdrawing'through the porous l5 cathode catholyte containing the caustic alkali;

said anode and cathode both having a porosity between 35% and 70% and an air permeability above 15 and comprising comminuted solid carbon embedded in a porous carbon binder having 20 uniformly distributed pores.

GEORGE W. HEISE.

nnwm A. SCHUMACHER. 

